JPS6330924B2 - - Google Patents

Description

[Detailed description of the invention] The present invention provides a temperature range of 30 to 180°C in a temperature range of 150 to 200°C.
The present invention relates to a thermosetting resin composition for molding, which has fast curing properties that can be cured in seconds, and in which the cured product has a low modulus of elasticity, a low coefficient of expansion, a high glass transition point, excellent heat resistance, and flexibility. In recent years, in the field of electronic components, with the aim of reducing size, weight, and reliability, there has been a trend towards increasing the size of semiconductor element pellets and increasing their functionality by combining active and passive elements. Therefore, there is a strong demand for resin materials for molding various elements to have the property of having a small effect of stress on inserts even when directly molded. Conventionally, epoxy-based, silicone-based,
Materials such as phenolic and diallyl have been used. Among these, epoxy resin compositions whose curing agent is phenol novolac resin obtained by condensation reaction of phenol and formaldehyde under an acidic catalyst are superior in that they have well-balanced adhesion to inserts, electrical properties, etc. , has become the mainstream resin for molding. However, if this type of resin composition is directly molded with the resin without applying a flexible protective coat to the element pellet, the element pellet may crack or the bonding wires may be cut. Faults due to stress on the insert and metal inserts (leads, frames, etc.)
Due to lack of adhesion or adhesion of the molding resin to (including elements, etc.), moisture infiltrates from the interface between the two, leading to problems such as corrosion and breakage of aluminum electrodes or bonding wires. As a countermeasure against this, it is important to reduce the stress exerted on the insert and improve the adhesion and adhesion between the insert and the mold resin. From this point of view, molds that have excellent adhesion and adhesion to metals such as gold, aluminum, silver, nickel, and cobalt, and have a low elastic modulus, low expansion coefficient, and high glass transition temperature for cured products. Development of resin compositions is required. Addition of a flexibilizing agent may be considered as one means for improving the adhesion and adhesion of the molding resin and lowering the modulus of elasticity. However, when this method is adopted, the glass transition point of the cured resin is lowered, making it difficult to obtain a highly reliable molded product. The present invention was made in view of the above-mentioned situation, and its purpose is to provide a material with excellent adhesion and adhesion to inserts, low elastic modulus, and low expansion coefficient.
Moreover, it is an object of the present invention to provide an epoxy resin composition having a high glass transition point of 140°C or higher. In addition, from the perspective of production rationalization of the molding process,
The object of the present invention is to provide a fast-curing epoxy resin composition that can be cured at 150-200°C in 30-180 seconds. A feature of the present invention is that in a product containing a curing catalyst, an inorganic filler, and a thermosetting resin, the thermosetting resin contains (a) 1 equivalent of a polyfunctional epoxy compound, (b) 1 to 4 equivalents of a polyfunctional isocyanate compound ( c) General formula (1) HS-(C ₂ H ₄ -O-CH ₂ -O-C ₂ H ₄ -S-S)
n- -C ₂ H ₄ -O-C ₂ H ₄ -O-C ₂ H ₄ -SH (1) (in the formula, n is 3 to 10) with a molecular weight of about 500 to
The thermosetting resin composition for molding is characterized in that it comprises only 20 to 50 parts by weight of a polysulfide compound of 10,000 to 100 parts by weight of the epoxy compound. In other words, it is a molding resin that is composed of only the three components (a), (b), and (c) above and does not contain anything else as a resin component, giving a cured product with excellent heat resistance and low elastic modulus. The composition can be provided. In the present invention, examples of the polyfunctional epoxy compound include dicrycidyl ether of bisphenol A, butadiene diepoxide, 3,4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexanecarboxylate, vinylcyclohexane dioxide, 4, 4′-di(1,2-
epoxyethyl) diphenyl ether, 4,4'-
(1,2-epoxyethyl)biphenyl, 2,2
-Bis(3,4-epoxycyclohexyl)propane, glycidyl ether of resorcinol, diglycidyl ether of phloroglucin, diglycidyl ether of methylphloroglucin, bis-(2,
3-Epoxycyclohentyl)ether, 2-
(3,4-epoxy)cyclohexane-5,5-
Spiro(3,4-epoxy)-cyclohexane-
m-dioxane, bis-(3,4-epoxy-6
-methylcyclohexyl)adipate, N,
N′-m-phenylene bis(4,5-epoxy-
Difunctional epoxy compounds such as dicarboximide (1,2-cyclohexane), triglycidyl ether of para-aminophenol, polyallyl glycidyl ether, 1,3,5-tri(1,2-epoxyethyl)benzene, 2,2' , 4,4'-tetraglycidoxybenzophenone, tetraglycidoxytetraphenylethane, polyglycidyl ether of phenol formaldehyde novolak,
Triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, etc.3
Epoxy compounds with higher functionality are used. Further, the polysulfide-based low molecular weight polymer ( ) in the present invention has the general formula HS-(C ₂ H ₄ -O-CH ₂ -O-C ₂ H ₄ -S-S)
n _{- C2H4 -} O- _C2H4 -O- _{C2H4 -} SH is a polymer with a molecular weight of about 500 to 10,000 represented by n=3 to 10,
These are commercially available from Toray Chicor Co., Ltd. and others. In the present invention, methane diisocyanate and butane-1,1 are used as polyfunctional isocyanate compounds.
Diisocyanate, ethane-1,2-diisocyanate, butane-1,2-diisocyanate, transvinylene diisocyanate, propane-
1,3 diisocyanate, butane 11,4-diisocyanate, 2-butene-1,4-diisocyanate, 2-methylbutane-1,4-diisocyanate, pentane-1,5-diisocyanate, hexane-1,6-diisocyanate, heptane-
1,7-diisocyanate, octane-1,8-
Diisocyanate, nonane-1,9-diisocyanate, decane-1,10-diisocyanate, dimethylsilane diisocyanate, diphenylsilane diisocyanate, ω,ω'-1,3-dimethylbenzene diisocyanate ω,ω'-1,4-
Dimethylbenzene diisocyanate, ω, ω′-
1,3-dimethylcyclohexane diisocyanate, ω,ω'-1,4-dimethylcyclohexane diisocyanate, ω,ω'-1,4-dimethylbenzene diisocyanate, ω,ω'-1,4-
Dimethylnaphthalene diisocyanate, ω,
ω'-1,5-dimethylnaphthalene diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, zinclohexylmethane-4,4'-diisocyanate, 1,3-phenylene diisocyanate 1,4-phenylene Diisocyanate, 1-methylbenzene-2,4-diisocyanate, 1-methylbenzene-2,5-diisocyanate, 1-methylbenzene-2,6-diisocyanate, 1-
Methylbenzene-3,5 diisocyanate, diphenyl ether-4,4'-diisocyanate, diphenyl ether-2,4'-diisocyanate,
naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, biphenyl-
4,4'-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 2,3'-
Dimethoxybiphenyl-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenylmethane-4,
Difunctional isocyanates such as 4'-diisocyanate, 4,4'-dimethoxydiphenylmethane-3,3'-diisocyanate, diphenylsulfite-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate Compound, polymethylene polyphenyl isocyanate, triphenylmethane triisocyanate, tris(4-phenyl isocyanate thiophosphate), 3,
A trifunctional or higher functional isocyanate compound such as 3',4,4'-diphenylmethanetetrisocyanate is used. Furthermore, by using dimers of these isocyanate compounds, the storage stability and moisture resistance of the material can be further improved. In addition, in the present invention, a diisocyanate compound having a uretdione ring in the molecule is a compound having at least one uretdione ring in the molecule and having a chemical structure as shown in the following formula. (In the formula, R, R ₁ and R ₂ represent an arylene group or a substituted marylene group, and may be different from each other or partially or entirely the same). Examples of such compounds include 1,3-
bis(3-isocyanate-o-tolyl)-2,
4-uretdione, 1,3-bis(3-isocyanate-p-tolyl)-2,4-uretdione,
1,3-bis(3-isocyanate-4-methoxyphenyl)-2,4-uretdione, 1,3-
Examples include bis[4-(4-isocyanatephenylmethyl)phenyl]-2,4-uretdione. Further, in the present invention, various catalysts can be added for the purpose of promoting the curing reaction of the polyfunctional epoxy compound, and examples of the catalyst include triethanolamine, tetramethylbutanediamine, tetramethylpentanediamine, Tertiary amines such as tetramethylhexanediamine, triethylenediamine and dimethylaniline, oxyalkylamines such as dimethylaminoethanol and dimethylaminopentanol, and amines such as tris(dimethylaminomethyl)phenol and methylmorpholine can be applied. can. In addition, for the same purpose, as a catalyst, for example, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, dodecyltrimethylammonium iodide, trimethyldodecylammonium chloride, benzyldimethyltetradecylammonium chloride, benzylmethylpalmitylammonium chloride, allyldodecyltrimethylammonium bromide , benzyldimethylstearylammonium bromide, stearyltrimethylammonium chloride and benzyldimethyltetradecylammonium acetate, and further quaternary ammonium salts such as 2-undecylimidazole, 2-methylimidazole, 2-ethylimidazole can be applied. , 2-heptadecylimidazole, 2-
Methyl-4-ethylimidazole, 1-butylimidazole, 1-propyl-2-methylimidazole, 1-benzyl-2-methylimidazole,
1-cyanoethyl-2-methylimidazole, 1
-cyanoethyl-2-undecylimidazole,
1-cyanoethyl-2-phenylimidazole,
Imidazole compounds such as 1-azine-2-methylimidazole and 1-azine-2-undecylimidazole, or triphenylphosphine tetraphenylborate, triethylaminetetraphenylborate, N-methylmorpholinetetraphenylborate, pyridinetetra Phenylborate, 2-ethyl-4-methylimidazole tetraphenylborate and 2-ethyl-1,4-
Tetraphenylboron salts such as dimethylimidazole tetraphenylborate are useful. Two or more of the above catalysts can be used in combination. In addition, in the present invention, depending on the use and purpose of use, mold release agents such as fatty acids and waxes, known coupling agents such as epoxysilane, vinylsilane, borane compounds and alkoxy titanate compounds, and further, Known flame retardants such as antimony, phosphorus compounds and halogens and halogen-containing compounds can be used. Each of the above ingredients is heated (70 to 80
°C) It is blended by kneading. Furthermore, if all the components are solid, a dry blending method may be employed in which the components are pulverized and then mixed. Furthermore, the resin composition of the present invention may contain known inorganic fillers, mold release agents, and the like. For example, zircon, silica, alumina, aluminum hydroxide, titania, zinc leather, calcium carbonate, magnesite, clay, kaolin, talc, silica sand, glass,
Fused silica glass, asbestos, mica, various whiskers, carbon black, graphite, inorganic fillers such as molybdenum disulfide, mold release agents such as higher fatty acids and wax, epoxy silane, vinyl silane, borane and alkoxy titanate compounds, etc. At least one coupling agent such as the above may be blended. Also, as necessary,
Flame retardant agents such as halogen-containing compounds, antimony oxide, and phosphorus compounds can be used. Next, the present invention will be explained in detail by giving examples. Examples 1 to 11 As an epoxy compound, orthocresol novolac type ECN1273 (manufactured by Ciba Corporation, epoxy equivalent;
225) To 100 parts by weight, 53 parts by weight, 106 parts by weight, and 212 parts by weight of diphenylmethane-4,4'-diisocyanate (MDI) were separately blended as an isocyanate compound. In these formulations, Thiokol LP-2 (manufactured by Toray Thiokol Co., Ltd., average molecular weight 4000, crosslinking rate 2%), Thiokol LP-2 are added as polysulfide compounds.
Three types of compounds, Thiokol LP-32 (manufactured by Toray Thiokol Co., Ltd.; average molecular weight 4000, crosslinking rate 0.5%) and Thiokol LP-31 (manufactured by Toray Thiokol Company; average molecular weight 7500, crosslinking rate 0.5%), were added in predetermined amounts. As a curing catalyst, 3 parts by weight of triethylamine tetraphenylborate (TEA-K), 1 part by weight of epoxy silane KBM403 (manufactured by Shin-Etsu Chemical) as a coupling agent, and 70% by weight of quartz glass powder as a filler based on the resin components. It was blended so that it would be. Spread this mixture in two rolls of 8 inch diameter for 40~
After kneading at 60°C for 5 minutes, the mixture was coarsely ground to obtain the desired material composition. Using this composition, 180℃, 3 minutes, 70Kg/
Test specimens with various characteristics and MOSLSI for testing were molded under cm ² conditions. The table shows the compositional characteristics and properties of each formulation. 【table】

Claims (1)

[Scope of Claims] 1. A product containing a curing catalyst, an inorganic filler, and a thermosetting resin, wherein the thermosetting resin contains (a) 1 equivalent of a polyfunctional epoxy compound, (b) 1 to 4 equivalents of a polyfunctional isocyanate compound. (c) General formula (1) HS—(C ₂ H ₄ —O—CH ₂ —O—C ₂ H ₄ —S—S)
n- -C ₂ H ₄ -O-C ₂ H ₄ -O-C ₂ H ₄ -SH (1) (in the formula, n is 3 to 10) with a molecular weight of about 500 to
1. A thermosetting resin composition for molding, comprising only 20 to 50 parts by weight of a polysulfide compound of 10,000 to 100 parts by weight of the epoxy compound.